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Passive sampling is an
environmental monitoring Environmental monitoring describes the processes and activities that need to take place to characterize and monitor the quality of the environment. Environmental monitoring is used in the preparation of environmental impact assessments, as well a ...
technique involving the use of a collecting medium, such as a man-made device or biological
organism In biology, an organism () is any living system that functions as an individual entity. All organisms are composed of cells (cell theory). Organisms are classified by taxonomy into groups such as multicellular animals, plants, and ...
, to accumulate chemical
pollutant A pollutant or novel entity is a substance or energy introduced into the environment that has undesired effects, or adversely affects the usefulness of a resource. These can be both naturally forming (i.e. minerals or extracted compounds like oi ...
s in the environment over time. This is in contrast to grab sampling, which involves taking a sample directly from the media of interest at one point in time. In passive sampling, average chemical concentrations are calculated over a device's deployment time, which avoids the need to visit a sampling site multiple times to collect multiple representative samples. Currently, passive samplers have been developed and deployed to detect toxic metals,
pesticide Pesticides are substances that are meant to control pests. This includes herbicide, insecticide, nematicide, molluscicide, piscicide, avicide, rodenticide, bactericide, insect repellent, animal repellent, microbicide, fungicide, and lampri ...
s,
pharmaceuticals A medication (also called medicament, medicine, pharmaceutical drug, medicinal drug or simply drug) is a drug used to diagnose, cure, treat, or prevent disease. Drug therapy (pharmacotherapy) is an important part of the medical field and rel ...
,
radionuclide A radionuclide (radioactive nuclide, radioisotope or radioactive isotope) is a nuclide that has excess nuclear energy, making it unstable. This excess energy can be used in one of three ways: emitted from the nucleus as gamma radiation; transfer ...
s,
polycyclic aromatic hydrocarbon A polycyclic aromatic hydrocarbon (PAH) is a class of organic compounds that is composed of multiple aromatic rings. The simplest representative is naphthalene, having two aromatic rings and the three-ring compounds anthracene and phenanthrene. ...
s (PAHs),
polychlorinated biphenyl Polychlorinated biphenyls (PCBs) are highly carcinogenic chemical compounds, formerly used in industrial and consumer products, whose production was banned in the United States by the Toxic Substances Control Act in 1979 and internationally by t ...
s (PCBs), and other organic compounds in water, while some passive samplers can detect hazardous substances in the air.


Theory and application

The underlying principle of passive sampling is the flow of contaminant molecules or ions from the sampling medium (air or water) onto a collecting medium (the passive sampler), due to Fick's first law of diffusion and, depending on the passive sampler, a greater
binding affinity In biochemistry and pharmacology, a ligand is a substance that forms a complex with a biomolecule to serve a biological purpose. The etymology stems from ''ligare'', which means 'to bind'. In protein-ligand binding, the ligand is usually a mol ...
of contaminants with the collecting medium as compared to the sampling medium. As a result, contaminants concentrate on the collecting medium over time until they reach equilibrium with the surrounding medium. The use of passive sampling provides time-averaged concentrations of contaminants over the sampler's deployment period. It is important to distinguish passive sampling from ''active sampling'', which has the same underlying principle but employs moving parts, such as pumps, to force the sampling medium onto a collecting medium. Passive sampling solely relies on
molecular diffusion Molecular diffusion, often simply called diffusion, is the thermal motion of all (liquid or gas) particles at temperatures above absolute zero. The rate of this movement is a function of temperature, viscosity of the fluid and the size (mass) of ...
and the sorbing or binding of contaminants to agents in the samplers, which is why passive sampling is also called ''diffusive sampling''. Passive sampling is also distinct from grab sampling, which is the collection of an air, water, or soil sample to analyze directly for contaminants. These samples represent a single point in time and provide information about contaminant concentration at one point in time, unlike passive sampling devices or organisms. Many different kinds of passive samplers have been developed and have sampled many different contaminants, including: *
Antibiotic An antibiotic is a type of antimicrobial substance active against bacteria. It is the most important type of antibacterial agent for fighting bacterial infections, and antibiotic medications are widely used in the treatment and prevention of ...
s *
Bisphenol The bisphenols () are a group of chemical compounds related to diphenylmethane. Most are based on two hydroxyphenyl functional groups linked by a methylene bridge. Exceptions include bisphenol S, P, and M. "Bisphenol" is a common name; the letter ...
s *
Dioxin Dioxin may refer to: * 1,2-Dioxin or 1,4-Dioxin, two unsaturated heterocyclic 6-membered rings where two carbon atoms have been replaced by oxygen atoms, giving the molecular formula C4H4O2 *Dibenzo-1,4-dioxin, the parent compound also known as ...
s *
Flame retardant The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source a ...
s *
Furan Furan is a heterocyclic organic compound, consisting of a five-membered aromatic ring with four carbon atoms and one oxygen atom. Chemical compounds containing such rings are also referred to as furans. Furan is a colorless, flammable, highly ...
s *
Nanoparticle A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 1 ...
s *
Oxyanion An oxyanion, or oxoanion, is an ion with the generic formula (where A represents a chemical element and O represents an oxygen atom). Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determine ...
s such as
phosphate In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid . The phosphate or orthophosphate ion is derived from phospho ...
s * Polybrominated diphenyl ethers (PBDEs) * Polycyclic aromatic hydrocarbons (PAHs) *
Polychlorinated biphenyls (PCBs) Polychlorinated biphenyls (PCBs) are highly carcinogenic chemical compounds, formerly used in industrial and consumer products, whose production was banned in the United States by the Toxic Substances Control Act in 1979 and internationally by t ...
*
Pesticide Pesticides are substances that are meant to control pests. This includes herbicide, insecticide, nematicide, molluscicide, piscicide, avicide, rodenticide, bactericide, insect repellent, animal repellent, microbicide, fungicide, and lampri ...
s *
Pharmaceutical A medication (also called medicament, medicine, pharmaceutical drug, medicinal drug or simply drug) is a drug used to diagnose, cure, treat, or prevent disease. Drug therapy (pharmacotherapy) is an important part of the medical field and re ...
s *
Radionuclide A radionuclide (radioactive nuclide, radioisotope or radioactive isotope) is a nuclide that has excess nuclear energy, making it unstable. This excess energy can be used in one of three ways: emitted from the nucleus as gamma radiation; transfer ...
s *Toxic metals (Such as
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...
,
zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
, and
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
)


Passive sampling in water

Several kinds of passive sampling devices exist for monitoring pollutants present in water. In addition to these devices, organisms, such as
mussel Mussel () is the common name used for members of several families of bivalve molluscs, from saltwater and Freshwater bivalve, freshwater habitats. These groups have in common a shell whose outline is elongated and asymmetrical compared with other ...
s, living in the environment also "passively sample" contaminants (
bioaccumulation Bioaccumulation is the gradual accumulation of substances, such as pesticides or other chemicals, in an organism. Bioaccumulation occurs when an organism absorbs a substance at a rate faster than that at which the substance is lost or eliminated ...
) and can be used to monitor water pollution (
biomonitoring In analytical chemistry, biomonitoring is the measurement of the body burden of toxic chemical compounds, elements, or their metabolites, in biological substances. Often, these measurements are done in blood and urine. Biomonitoring is performed ...
).


Chemcatcher

Chemcatcher can passively sample
inorganic In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...
pollutants (metals) and a wide range of
organic Organic may refer to: * Organic, of or relating to an organism, a living entity * Organic, of or relating to an anatomical organ Chemistry * Organic matter, matter that has come from a once-living organism, is capable of decay or is the product ...
pollutants. It is composed of a single-use disc, with or without a
membrane A membrane is a selective barrier; it allows some things to pass through but stops others. Such things may be molecules, ions, or other small particles. Membranes can be generally classified into synthetic membranes and biological membranes. B ...
, sealed into a plastic support. Types of receiving phases and membranes vary greatly, depending on the target chemicals to be sampled. Time-averaged water concentrations of many chemical pollutants can be determined as long as sampling rate and the water flow rate are known.


Diffusive gradients in thin films (DGT)

Diffusive gradients in thin films (DGT) samplers passively sample
ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
ic trace metals, as well as
antibiotic An antibiotic is a type of antimicrobial substance active against bacteria. It is the most important type of antibacterial agent for fighting bacterial infections, and antibiotic medications are widely used in the treatment and prevention of ...
s,
oxyanion An oxyanion, or oxoanion, is an ion with the generic formula (where A represents a chemical element and O represents an oxygen atom). Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determine ...
s,
bisphenol The bisphenols () are a group of chemical compounds related to diphenylmethane. Most are based on two hydroxyphenyl functional groups linked by a methylene bridge. Exceptions include bisphenol S, P, and M. "Bisphenol" is a common name; the letter ...
s, and
nanoparticle A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 1 ...
s in different configurations. They are composed of plastic pistons and caps, with a window that exposes a binding gel, diffusive gel, and filter membrane to the sampling water. They can be used in both freshwater and marine environments, as well as in the water located between freshwater and marine
sediment Sediment is a naturally occurring material that is broken down by processes of weathering and erosion, and is subsequently transported by the action of wind, water, or ice or by the force of gravity acting on the particles. For example, sand an ...
particles, called ''pore water'' or ''interstitial water''. Once the mass of accumulated contaminants on the DGT sampler is known, the DGT equation (based on
Fick's law Fick's laws of diffusion describe diffusion and were derived by Adolf Fick in 1855. They can be used to solve for the diffusion coefficient, . Fick's first law can be used to derive his second law which in turn is identical to the diffusion eq ...
) can be used to calculate the time averaged water concentration of contaminants.


Microporous polyethylene tubes (MPT)

Microporous polyethylene tubes (MPT) attempt to mitigate the flow-dependency of other kinetic passive samplers such as Chemcatcher and POCIS by introducing a thicker membrane. The diffusive polyethylene layer prevents the thickness of the water-boundary layer (which is affected by flow) from dominating diffusion. The tube is filled with sorbents depending on the chemicals or chemical groups being sampled and has been successfully used to sample glyphosate, AMPA, illicit drugs and pharmaceuticals and personal care products.


Peepers

Peepers are passive
diffusion Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical p ...
samplers used for metals in freshwater and marine
sediment Sediment is a naturally occurring material that is broken down by processes of weathering and erosion, and is subsequently transported by the action of wind, water, or ice or by the force of gravity acting on the particles. For example, sand an ...
pore water, so they can be used to find areas that may have metal-contaminated sediments. Peepers are plastic vessels filled with clean water and covered in a dialysis membrane, which allows metals in sediment pore water to enter the water inside the peeper. They are usually placed deep enough into sediment to be in an
anoxic The term anoxia means a total depletion in the level of oxygen, an extreme form of hypoxia or "low oxygen". The terms anoxia and hypoxia are used in various contexts: * Anoxic waters, sea water, fresh water or groundwater that are depleted of diss ...
environment, in which metals will be soluble enough to sample. If the peepers are deployed long enough so the sediment pore water and contained peeper water reach equilibrium, they can accurately provide metal concentrations in sampled sediment pore water.


Polar organic chemical integrative sampler (POCIS)

Polar organic chemical integrative samplers (POCIS) sample
polar Polar may refer to: Geography Polar may refer to: * Geographical pole, either of two fixed points on the surface of a rotating body or planet, at 90 degrees from the equator, based on the axis around which a body rotates * Polar climate, the c ...
organic contaminants with a log
octanol-water partition coefficient The ''n''-octanol-water partition coefficient, ''K''ow is a partition coefficient for the two-phase system consisting of ''n''-octanol and water. ''K''ow is also frequently referred to by the symbol P, especially in the English literature. It is a ...
(Kow) value that is less than 3. Examples of these types of chemicals include polar pesticides, pharmaceuticals,
illicit drugs The prohibition of drugs through sumptuary legislation or religious law is a common means of attempting to prevent the recreational use of certain intoxicating substances. While some drugs are illegal to possess, many governments regulate the ...
,
flame retardant The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source a ...
s, and drug
metabolite In biochemistry, a metabolite is an intermediate or end product of metabolism. The term is usually used for small molecules. Metabolites have various functions, including fuel, structure, signaling, stimulatory and inhibitory effects on enzymes, c ...
s. The POCIS is composed of variable numbers of solid sorbent discs attached to a support rod and encased in a metal cage, and has two possible sorbent configurations, the pesticide-POCIS and pharmaceutical-POCIS. As long as the amount of water passing over the sampler is known, polar organic contaminant water concentrations can be calculated after extracting sorbed contaminants from a POCIS.


Semipermeable membrane devices (SPMDs)

Semipermeable membrane devices (SPMDs) passively sample
nonpolar In chemistry, polarity is a separation of electric charge leading to a molecule or its chemical groups having an electric dipole moment, with a negatively charged end and a positively charged end. Polar molecules must contain one or more polar ...
organic contaminants with a log octanol-water partition coefficient (Kow) value greater than 3. Examples of these types of chemicals include polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs),
polybrominated diphenyl ethers Polybrominated diphenyl ethers or PBDEs, are a class of organobromine compounds that are used as flame retardants. Like other brominated flame retardants, PBDEs have been used in a wide array of products, including building materials, electronics, ...
(PBDEs), chlorinated pesticides,
dioxin Dioxin may refer to: * 1,2-Dioxin or 1,4-Dioxin, two unsaturated heterocyclic 6-membered rings where two carbon atoms have been replaced by oxygen atoms, giving the molecular formula C4H4O2 *Dibenzo-1,4-dioxin, the parent compound also known as ...
s, and
furan Furan is a heterocyclic organic compound, consisting of a five-membered aromatic ring with four carbon atoms and one oxygen atom. Chemical compounds containing such rings are also referred to as furans. Furan is a colorless, flammable, highly ...
s. SPMDs are composed of sealed plastic tubing filled with
triolein Triolein is a symmetrical triglyceride derived from glycerol and three units of the unsaturated fatty acid oleic acid. Most triglycerides are unsymmetrical, being derived from mixtures of fatty acids. Triolein represents 4–30% of olive oil. Tr ...
, in which nonpolar organics are very soluble and which serves as a representation of the fatty tissues of aquatic organisms. The tubing is then weaved between metal rods and enclosed in a metal cage. The sampler can be made in varying lengths of tubing for different applications, since sampling rate depends on the surface area of tubing exposed to the water. As long as the amount of water passing over the sampler is known, nonpolar organic contaminant water concentrations can be calculated after extracting contaminants from a SPMD.


Stabilized liquid membrane devices (SLMDs)

Stabilized liquid membrane devices (SLMDs) passively sample
ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
ic metals in freshwater. They are made of
low-density polyethylene Low-density polyethylene (LDPE) is a thermoplastic made from the monomer ethylene. It was the first grade of polyethylene, produced in 1933 by Imperial Chemical Industries (ICI) using a high pressure process via free radical polymerization. Its ...
plastic tubing sections that are sealed on both ends and filled with an equal mixture of
oleic acid Oleic acid is a fatty acid that occurs naturally in various animal and vegetable fats and oils. It is an odorless, colorless oil, although commercial samples may be yellowish. In chemical terms, oleic acid is classified as a monounsaturated omega ...
and metal
chelating agent Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These ligands are ...
. They work by interacting with calcium and magnesium ions in freshwater, which forms a hydrophobic film on the outside the SLMD plastic membrane in which the chelating agent can bind to metals in the sampling water. They have been deployed for up to month-long periods in the field, alone or covered by a plastic tube housing to mediate water flow. Metal weight accumulated by a SLMD over its deployment period can be calculated and divided by the SLMD deployment time to get an average metal weight accumulated per time unit, but currently, no method has been developed to convert this to an average metal concentration. In addition, SLMD sampling rates greatly vary with water flow rate, which plastic housings can be used to control.


Passive sampling in air

Passive sampling can also be accomplished for contaminants in the air, including airborne particles and hazardous vapors and gases. This can be done with man-made devices or with biomonitoring organisms, such as
lichens A lichen ( , ) is a composite organism that arises from algae or cyanobacteria living among hypha, filaments of multiple fungus, fungi species in a mutualism (biology), mutualistic relationship.


Sorbent tubes

Sorbent tubes are passive samplers for
volatile organic compound Volatile organic compounds (VOCs) are organic compounds that have a high vapour pressure at room temperature. High vapor pressure correlates with a low boiling point, which relates to the number of the sample's molecules in the surrounding air, a ...
s (VOCs). They are glass tubes filled with adsorbing materials, such as
charcoal Charcoal is a lightweight black carbon residue produced by strongly heating wood (or other animal and plant materials) in minimal oxygen to remove all water and volatile constituents. In the traditional version of this pyrolysis process, cal ...
or
silica gel Silica gel is an amorphous and porous form of silicon dioxide (silica), consisting of an irregular tridimensional framework of alternating silicon and oxygen atoms with nanometer-scale voids and pores. The voids may contain water or some other l ...
, which the air to be sampled passes through. The adsorbing materials remove VOCs from the air that passes through them, and the VOCs can be desorbed and analyzed. Air concentrations can be calculated using the amount of air that flowed through the sorbent tube and the amount of contaminants desorbed.


Advantages

Contaminant concentrations from passive sampling reflect average contamination throughout the sampler deployment time, meaning the sample will capture contaminant concentration fluctuations over the whole deployment period. Traditional grab sampling does not do this, since collected samples only represent a single moment in time and multiple grab samples must be taken to observe variation in contaminant concentrations over time. This integrative sampling method can also can result in the detection of chemicals present at such low concentrations that they would be undetected in a grab sample, due to concentration of the chemicals on the sampler over time. As a result, passive sampling has the potential to be a less time-intensive, less expensive and more accurate sampling method than grab sampling. In addition, passive samplers are often easy to use and deploy, have no pumps or moving parts, and do not require electricity, since they rely on the
molecular diffusion Molecular diffusion, often simply called diffusion, is the thermal motion of all (liquid or gas) particles at temperatures above absolute zero. The rate of this movement is a function of temperature, viscosity of the fluid and the size (mass) of ...
of contaminants or binding of contaminants to agents within the samplers, unlike active sampling. They may also be inexpensive and simple to construct, such as SLMDs, which only require sealed plastic tubing and two chemical components. Passive sampling may also more accurately reflect metal concentrations that are
bioavailable In pharmacology, bioavailability is a subcategory of absorption and is the fraction (%) of an administered drug that reaches the systemic circulation. By definition, when a medication is administered intravenously, its bioavailability is 100%. Ho ...
to organisms than other sampling methods. For example, the
SPMD In computing, single program, multiple data (SPMD) is a technique employed to achieve parallelism; it is a subcategory of MIMD. Tasks are split up and run simultaneously on multiple processors with different input in order to obtain results fast ...
sampler uses a semipermeable membrane and
triolein Triolein is a symmetrical triglyceride derived from glycerol and three units of the unsaturated fatty acid oleic acid. Most triglycerides are unsymmetrical, being derived from mixtures of fatty acids. Triolein represents 4–30% of olive oil. Tr ...
(a
triglyceride A triglyceride (TG, triacylglycerol, TAG, or triacylglyceride) is an ester derived from glycerol and three fatty acids (from ''tri-'' and ''glyceride''). Triglycerides are the main constituents of body fat in humans and other vertebrates, as w ...
), both of which mimic
toxicant A toxicant is any toxic substance, whether man-made or naturally occurring. By contrast, a toxin is a poison produced naturally by an organism (e.g. plant, animal, insect). The different types of toxicants can be found in the air, soil, water, or ...
uptake by organism fatty tissue. However, this depends on the type of passive sampler used, since some samplers, such as peepers, rely solely on molecular diffusion, which may be too simple to be reflective of the complex processes of contaminant uptake in an organism.


Disadvantages

Since passive sampling provides information about average contaminant concentrations, all possible concentrations over the sampler deployment time are included in this average value. However, there is no way of finding out the complete range of contaminant concentrations over the deployment time at a single site with only passive sampling. If high and low concentrations of contaminants throughout the sampling period are needed, other sampling methods should be used in conjunction with passive sampling. Not all passive samplers have universally accurate ways to convert contaminant masses accumulated into water concentrations, which are used in government regulation, such as the
United States Environmental Protection Agency The Environmental Protection Agency (EPA) is an independent executive agency of the United States federal government tasked with environmental protection matters. President Richard Nixon proposed the establishment of EPA on July 9, 1970; it be ...
Clean Water Act The Clean Water Act (CWA) is the primary federal law in the United States governing water pollution. Its objective is to restore and maintain the chemical, physical, and biological integrity of the nation's waters; recognizing the responsibiliti ...
.{{cite web , title=National Recommended Water Quality Criteria - Aquatic Life Criteria Table , url=https://www.epa.gov/wqc/national-recommended-water-quality-criteria-aquatic-life-criteria-table , publisher=United States Environmental Protection Agency , access-date=4 June 2018, date=2015-09-03 With some samplers, as with the DGT, this can be done using equations developed for the samplers, but not all samplers have these. Passive sampler deployment time is also limited depending on the sampler's capacity; for example, SLMDs have been deployed for month-long periods, but may reach saturation and stop sampling much sooner if metal concentrations and water flow rates are high enough. However, this issue is avoidable if literature on the relevant passive sampler is examined for background information about sampler capacity and ideal deployment times prior to deployment.


References

Environmental monitoring Sampling techniques